Neptunium solvent extraction process



. neutrons per fission,

. p 7 2,907,628 :NEPTUNIUM SOLVENT EXTRACTION LyleR. Dawson, Lexington, Ky., and Paul R. Fields, Chicago, 111., assignors to the United States of America as represented by th United States Atomic Energy -Commission,. I

No Drawing. "Application June 22 1949 Serial No.100,744

rnocnss Um 1 man 23 min.

This isotope of neptunium has a half-life of 2.33 days and by beta decay is converted to the plutonium isotope Pu M In addition to the production of neptunium and plutonium by neutron bombardment of uranium using a cyclotron, neutronic reactors have been developed for the production of neptunium, fission products from natural uranium by a self sustaining chain reaction. One of the isotopes of uranium occurring in natural uranium is amount of 0.71% by weight. When this isotope is bombarded by slow neutrons, preferably of thermal energies, it undergoes fission and releases on an average about two in addition to the production of fission fragments of relatively low atomic weights. The main constituent of natural uranium, namely, U absorbs thermal neutrons to produce Np and Pu as described above. Thus, in a natural uranium neutronic reactor the excess neutrons that are released by fission are sufiicient to maintain a production of neptunium and plutonium through neutron absorption by the predominant uranium isotope P However, the concentration of plutonium thus produced is generally small, rarely being above 1% by weight of the uranium and usually being substantially below this concentration. Thus, it is necessary to recover neptunium, plutonium, and fission products from uranium masses from neutronic reactors having neptunium, plutonium, andfission product concentrations below one part per thousand parts and even one part per million parts of uranium.

As mentioned above, during neutron-irradiation of uranium there is produced in addition to the transuranic elements, Np and Pu, other elements, of lower atomic weight, known as fission fragments. These radioactive fission fragments are composed of two distinct groups of plutonium, and desirable United States Patent Patented Oct. 6, 1959 ice The various radioactive fission products have half-lives that range from a fraction of a second to thousands of U and it is present in the years. Those having very short half-lives may be substantially eliminated by aging the neutron-irradiated material for a reasonable period of time before further processing. Thoseradioactive fission products having very long halflives do not have a sufiiciently intense radiation to endanger personnel protected by moderate shielding. On the other hand, the radioactive fission products that have half-lives ranging from a few days to a few years have dangerously intense radiations which cannot be eliminated by aging for practical storage periods. The fission products of the last described class are chiefly the radioactive isotopes of Sr, Y, Zr, Cb, and Ru of the light group and Te, 1, Cs, Ba, La, Ce, and Pr of the heavy group.

During the operation of the neutronic reactor, i.e., a chain-reacting uranium-graphite-pile, another isotope of neptunium, namely Np is produced. It is an alphaemitter witha half-life of about 2.2 10 years. By aging of the irradiated uranium, the concentration of Np since it has a half'life of 2.33 days, becomes very small.

Various processes have been developed for separating neptunium from uranium and from plutonium whereby aqueous solutions of neptunium salts are obtained, especially such solutions also containing fission products.

An object of this invention is to provide a process for the separation ofneptunium from an aqueous solution containing a neptunium salt.

A second object of the present invention is to separate nept 'um from its mixture with fission products.

Another object of this invention is to provide a method for separating neptunium from its solution in the organic solvent used to extract neptunium from aqueous solutions.

Other objects of this invention will be apparent from the description which follows.

We have found that neptunium values can be separated atrom aqueous solutions of a neptunium nitrate containing nitric acid and a salting-out agent by extracting the neptunium nitrate using a liquid organic solvent that has an atom capable of donating an electron pair to a coordination bond. 7

There are several types of organic compounds that are satisfactory solvents for the extraction of a neptunium elements, namely, a light element group and a heavy elefragments and the resulting decay products are collectively known as fission products.

nitrate from an aqueous solution containing a salting-out agent. These types are ethers, glycol ethers, esters, ketones, alcohols, alkyl phosphates, nitrohydrocarbons, and alkyl sulfides. A common structural property of all of these types of compounds is that they have an atom capable of donating an electron pair to a coordination bond. The extractive solvent is a liquid substantially immiscible with water and aqueous solutions. If it is a solid at room temperature, the extraction is carried out at a temperature above its melting point. The following is a list of compounds that are suitable extractants for the separation of a neptunium nitrate from aqueous nitric acid solutions containing a salting-out agent:

Carbitol acetate) (hexone) i Tributyl phosphate 3 Trioctyl phosphate Dioctyl hydrogen phosphate Octadecyl dihydrogen phosphate Nitromethane Ethyl sulfide n-Propyl sulfide Alkyl phosphates have the general formula:

30 RO P=O Where R is a member of the group consisting of a hydrogen atom and an alkyl radical and R is an alkyl water-immiscibility.

In addition to using the individual solvents the present invention contemplates the use of solvents that are mix- Diethyl V solvents for this process. In the foregoing list of classes of suitable organic solvents the compounds contain an oxygen atom or a sulfur atom capable of donating a pair of electrons to a coordination bond.

The neptunium nitrates suitable for extraction by the foregoing solvents are the nitrates of neptunium in the are Np(NO and NpO (NO respectively, and the latter nitrate is preferred.

The aqueous solution used for which salt is itself unextractable by the organic solvent of this invention. The following compounds are examples of suitable salts: NaNO Ca(NO KNO s)z LiNos, a)2 Q Ii: I a)a, Mn(NO and Al-(NO The molar concentration of the salting-out agent will depend upon the valence of the nitric acid, and a nitrate salting-out agent by contacting the solution with an organic solvent of the type described above. It is preferable that the contact time be suflicient for an equilibrium of the neptunium and after separating the two phases to contact the organic extract phase. The two aqueous extract phases are combined for maximum yield of neptunium salt.

Another embodiment consists only of the extraction of a neptunium nitrate from its solution in an organic solvent of the type disclosed above by contacting with Water and separating an organic solvent phase and an aqueous extract phase.

The volume ratio of aqueous solution to organic'solvent may be varied Widely, e.g., between 10:1 and 1:10. The ratio of organic solvent to water in the re-extraction also may be varied widely.

The following examples, taken alone and in combination, are illustrative of the various embodiments of this invention. While the examples used N13 they are illustrative, of course, of the invention for the other iso topes of neptunium.

EXAMPLE I of pentaand hexavalent neptunium, namely, and NpO (NO 0.316 ml. of concentrated nitric acid; and 0.06 ml. of water. The final solution was 2 ml. of 8 N nitric acid containing 25 mg./ml. of trivalent bismuth, and approximately 9.4 10 beta counts/min. (about 25% geometry) due to Np Ammonium hexanitratocerate was added to a 1-ml. sample of this solution in sufiicient amount to impart a greenish-yellow color to the solution. This compound oxidized pentavalent hexavalent state. Ammonium nitrate of ammonium nitrate was added to the other l-ml. sample ammonium hexanitratocerate.

distilled water in a the volume of the '77 1 Based on N p content of original aqueous-solution.

Table I N an Organic Solvent Used EXAMPLE n A,2-m1. quantityof 8 N nitric acid containing 25. mg./ml. of trivalent bismuth as bismuth nitrate, Np tracer, and fission products in tracer quantities was prepared. The Np concentration was about the same as in Example I. Ammonium hexanitratocerate was added to a 1-ml. quantity of the solution followed by ammonium nitrate addition and ether extraction as in Example I. Ammonium nitrate was added to the other l-ml. sample as in Example I followed by methyl isobutyl ketone extraction. In each experiment after the third cycle, the organic solvent layer was shaken for ten minutes with 1.5 ml. of distilled water. The water layer was frozen and organic solvent was poured back into the first flask. One more extraction cycle was carried out using this 1.5 m1. quantity of water to wash the organic solvent for reextraction of neptunium values. The aqueous raftinate phase, the organic solvent phase and the two aqueous extract phases were analyzed for beta-activity. The extraction and re-extraction data are presented in Table II.

Table II Percent Percent Np in- Np Organic Solvent Used Extracted by Organic 1st Aq. 2nd Aq.

Solvent Extract 1 Extract 1 Diethyl ether 97. 4 86. 2 10.1 Methyl isobutyl ketone 89. 4 72. 5 16. 8

l Based on Np content oi original aqueous solution.

The data show the value of the aqueous re-extraction for maximum recovery of. neptunium from the organic solvent phase. The data also show the fission products do not impair the extraction and re-extraction efficiencies.

EXAMPLE 111 Two experiments were carried out in a similar manner to those described in Example I1 except no fission products were present and the nitric acid concentration was only 2 N after ammonium nitrate addition, i.e., the concentration was only one-half the concentration used in Example II. Ammonium hexanitratocerate was used for oxidizing pentavalent neptunium to the hexavalent state in the methyl isobutyl ketone experiment, as well as in the ether experiment. Each initial aqueous solution contained 235x counts/min. (about 25% geometry) of Np The extraction data are presented below in Table III.

Table 111 Percent Percent Np inm Organic Solvent Used Extracted by Organic 1st Aq. 2nd Aq.

Solvent Extract 1 Extract 1 f Diethyl ether 99. 6 94. 1 5. 7 Methyl isobutyl ketone 99. 9 97 2. 9

1 Based on Np content of original aqueous solution.

EXAMPLE IV A Z-ml. quantity of 4 N nitric acid containing only 12.5 mg./ml. of Bi(IIl) and a tracer concentration of a mixture of salts of pentaand hexa'vailent neptunium was prepared. A l-ml. portion was oxidized by the addition of ammonium hexanitratocerate. Ammonium nitrate was added to both l-ml. portions as in the previous examples and the resulting solutions were extracted with methyl isobutyl ketone with re-extraction to produce two aqueous extract phases as in Example III, No fission products were present. The extraction data are presented below in Table IV.

6 Table IV Percent Np' in- 7 Percent Ce(IV) Used No -L Yes 1 Based on Np content of original aqueous solution.

EXAMPLE v A l-ml. quantity of nitrates of pentavalent a tracer solution of a mixture of and hexaivalent neptunium and containing 4 N nitric acid and 12.5 mg./ml. of Bi(III) was oxidized by the addition of ammonium hexanitratocerate. Ammonium nitrate was added to produce a 10 N ammonium nitrate solution which was extracted for ten minutes with three times its volume of hexone. The mixture was put in a freezing bath and the water layer frozen. The hexone layer was poured into a 10-ml. buret and 10 ml. ofan aqueous solution containing 10 M ammonium nitrate was slowly passed through hexone. The original solution contained 5.46 10' beta counts/ min. (about 25% geometry). Analyses of the aqueous raffinate layer, the hexone layer after washing with the ammonium nitrate solution, and the ammonium nitrate wash solution showed that 97.4% of the neptunium was extracted by the hexone and only 0.7% (based on total neptunium content) was removed from the hexone solution by the ammonium nitrate wash.

EXAMPLE VI An aqueous solution containing tracer concentrations of salts of fission products was prepared. The concentrations of nitric acid,,jainmonium nitrate, and Bi(NO were the same as in Example IV. The aqueous solution contained no Np No ammonium hexanitratocerate was used. The solution was extracted with hexone and the hexone was'extracted with water as in Example IV. The initial aqueous solution contained 2.96 10 beta counts/min. and 5.14 10 gamma counts/min. Analyses of the various layers showed that hexone extracted less than 1% of the beta-emitting fission products and less than 0.1% of'the gamma-emitting fission products.

EXAMPLE. VII

An aqueous solution containing 1 M nitric acid and a tracer mixture of the nitrates of pentaand hexavalent Np was prepared. The beta counts/min./ml. (about 25% geometry) due to Np were 19,690. A l-ml. aliquot was saturated with sulfur dioxide and then made 10 M in ammonium nitrate. The resultant solution was shaken vigorously for ten minutes with three times its volume of hexone. The aqueous and hexone layers were allowed to separate and the hexone layer was removed and evaporated under vacuum over 1 ml. of dilute nitric acid. The resultant dilute nitric acid solution was analyzed for neptunium to determine the degree of hexone extraction. Anotherl-ml. portion of the original solution was made 0.2 M in hydroxylamine instead of saturating with sulfur dioxide.- After making 10 M in ammonium nitrate, the solution was extracted with hexone as in the case of the sulfur dioxide-saturated solution. Hexone extracted 26.4% of the neptunium from the suliurdioxide-saturated solution whereas hexone extracted only 2.2% of the neptunium from the aqueous solution treated with the hydroxylamine. Sulfur dioxide reduces both hexaand pentavalent neptunium to tctravalent neptunium which is fairly extractable as indicated. The amount of neptunium extraction can be increased by increasing the acidity of the ammonium nitrate solution and by increasing the number of extraction cycles. Hydroxylamine merely reduces hexavalent neptunium to out using well-known pentavalent neptunium and its nitrate is not as extractable as tetraand hexavalent neptunium.

EXAMPLE VIII One pound of uranyl nitrate hexahydrate Was placed in a neutr'onic reactor to produce Np The sample a slurry The aqueous and the precipitate washed and reand it was centrifuged for ten minutes. layer was removed acid was added to produce a lanthanum The solution wascentrifuged and tate was washed. This lanthanum fluoride fluoride prethe precipiwarmed to oxidize The final volume was about ml. was added in the amount of 1.6 g./ml. of solution thereby of stirring the two solutions vigorously for ten minutes followed by a three-minute Ice. After the aqueous layer froze,

poured into a second flask containing ml. of distilled water. The contents of the second flask were stirred vigorously for ten minutes and the contents allowed to settle for five minutes. extract layer was frozen and the ether poured back into the first flask to continue the extraction cycle. total of three extraction cycles, the aqueous extract phase was heated to remove any dissolved ether. aqueous extract solution contained practically all of the neptunium originally present in the neutron-irradiated uranyl nitrate hexahydrate. The Np recovered had a beta-activity of 2.7 10 counts/minute (about geometry).

Similar recoveries were made of Np from neutronirradiated uranyl nitrate hexahydrate using ammonium hexanitratocerate as the oxidizng agent instead of potassium permanganate and using methyl isobutyl ketone 01" ether. Aluminum nitrate and other compounds capable of complex fluoride ions are suitable substitutes for zirconyl nitrate to dissolve lanthanumfluoride. Potassium dichromatef was another oxidizing agent used for converting pentavalent neptunium to hexavalent neptunium before solvent extraction.

The process of the present invention may be carried extraction procedures and appa- Thus, the extraction steps may be eifected by the use of batch, continuous batch, batch countercurrent or continuous countercurrentmethods. In column operation the organic solvent may be either the dispersed phase or the continuous phase.

The foregoing illustrations andembodiments of this invention are not intendedtolimit its scope, which is to be limited entirely by the appended claims.

What is claimed is:

1. In the process of separating neptunium values from an aqueous solution comprising nitric acid, nitrates of fission products, and neptunium nitrate wherein a salting-out agent is added, an oxidizing agent .is added to the hexavalent state, and then bringing the aqueous solution into contact with a sub- 2. A process of separating neptunium values from an aqueous solution comprising nitric acid, neptunium nitrate,

References Cited in the file of this patent UNITED STATES PATENTS 2,227,833

OTHER REFERENCES Fischer et al.: Ein Neues Verfahren zur Trennung der Seltenen Erden, Naturwissenschaften, vol. 25, p. 348 (1937).

Seaborg: The Chemical and Radioactive Properties of the Heavy Elements, Chemical and Engineering News, vol. 23, No. 23, pp. 2190-2193 (1945).

Katzin et al.: Theoretical Consideration of the Ether Extraction of Uranyl Nitrate From Aqueous Solutions Containing Various Metal Nitrate Salting Agents, AECD-2758, November 20, 1947 (declassified 1949). Technical. Information Division, Atomic Energy Commission, Oak Ridge, Teun.

Katz et aL: The Chemistry of the Actinide Elements, p. 419 (1957 

1. IN THE PROCESS OF SEPARATING NEPTUNIUM VALUES FROM AN AQUEOUS SOLUTION COMPRISING NITRIC ACID, NITRATES OF FISSION PRODUCTS, AND NEPTUNIUM NITRATE WHEREIN A SALTING-OUT AGENT IS ADDED, AN OXIDIZING AGENT IS ADDED TO RAISE THE NEPTUNIUM TO THE HEXAVALENT STATE, AND THEN BRINGING THE AQUEOUS SOLUTION INTO CONTACT WITH A SUBSTANTIALLY WATER-IMMISCIBLE LIQUID ORGANIC SOLVENT AND THEN SEPARATING THE RESULTING AQUEOUS PHASE AND THE RESULTING ORGANIC SOLVENT EXTRACT PHASE CONTAINING SAID NEPTUNIUM NITRATE, THE IMPROVEMENT CONSISTING OF CARRYING OUT SAID CONTACT AT A NITRIC ACID CONCENTRATION OF ABOUT 2 N. 